Method of manufacturing solid alcohols



United States Patent 3,247,264 METHOB or MANUFACTURING some ALcorroLsWarren L. Beears, Brecksviiie, and Edward H. Eoliinger, Akron, Qhio,assignors to Goodrich-Gulf Chemicals, 1116., Cievcland, Ohio, acorporation of Deiaware No Drawing. Fiied July 22, 1960, Ser. No. 44,525

153 (Jiaims. (Cl. 260632) This invention relates to a process forproducing telomer alcohols from oxidized alkyl aluminum chlorides, andparticularly for producing telomer alcohols having from 12 to 30 carbonatoms from mixed oxidized telomer allryl aluminum chlorides, commonlyreferred to in the art as mixed telomer allroxyaluminum chlorides, whichprocess constitutes an essential step in the production of telomeralcohols directly from alpha-olefins, such as ethylene, by chemicallyinserting hydrocarbon groups into mixed alkyl aluminum chlorides bychain growth, that is, by telomerization, to produce mixed telomer alkylaluminum chlorides, the latter in turn being oxidized to produce mixedelomer alkoxyaluminum chlorides, and finally, the mixed telomeralkoxyaluminum chlorides are treated with a proton donator to convertthe mixed telomer alkoxyaluminurn chlorides to telomer alcohols havingthe same number of carbon atoms as are contained in the telomer alkylgroups of the mixed telomer alkoxyaluminum chlorides. It is to thisfinal step that the present process relates.

A preferred process for the production of telomer alcohols from gaseousalpha-olefins is disclosed in the copending application Serial No.22,702, filed April 18, 1960.

In that application, the process for producing telomer alcohols, towhich this invention relates, is fully set out. Briefly, it comprises aseries of coordinated steps represented by the following equations:

3C H Cl+2Al Z (C H AlCl l 2 z s xA C 2 4 n an+1)x 2 n 2u+1)X y l" 2 11'2n+l )x y (C,,H O) AlCl +xH+ xC l-1 OH-}- (4) wherein x and y representaverage numerical values ranging from 2.7 to 0.3 and whose sum is 3; mrepresents the number of moles of (3 1-1 groups required for reaction(2); n represents the average number of carbon atoms built into thealkyl chains of the mixed alkyl aluminum chlorides to produce the mixedtelomer alkyl aluminum chlorides, and which for plasticizers normallyranges from 8 to 16 carbon atoms, and for other industrial use, such asdetergents, ranges from 12 to 30 carbon atoms, and even a larger numberof carbon atoms are desired for some industrial uses.

In each of the above Equations 1 to 4, x and y represent the averagenumerical values of the constituents of the mixed reaction products.Thus, Where x and y are 1.5, the compounds are termed sesquichlorides.However, the values of x and y are commonly of the order of 1.8 to 1.2,and, as indicated above, may vary as widely as from 2.7 to 0.3, or evenmore widely. In the chemical industry, independently of the specificnumerical values of x and y, the mixed alkyl aluminum chlorides ofEquations 1 to 4 above, are termed sesquichlorides, and the termsesquichloride is sometimes herein used in that broad sense.

It is to the step (4) above, namely, the hydrolysis of the mixedoxidized telomer alkyl aluminum chlorides, or the telomer alkoxyaluminumsesquichlorides, by a proton donator, to produce the telomer alcohols,that the invention of this application primarily relates.

As described in the earlier copending application, Ser. No. 22,702, themixed telomer alkoxyaluminum chlorides 3,247,264 Patented Apr. 19, 1966which are to be hydrolyzed to form the telomer alcohols and which areproduced by the oxidation of mixed telomer alkyl aluminum chlorides, asin Equation 3 above, (a) may be of high purity, the other chemicalcompounds present during the oxidation reaction (3) having been removedprior to the hydrolysis, or (b) may contain some or all of the compoundspresent during the oxidation reaction (3), namely (i) liquid organicanhydrous dispersant or dispersants, (ii) finely divided potassium salt,and (iii) free hydrocarbons. In either case, the hydrolyzed mixedtelomer alkoxyaluminum chlorides, or telomer alcohols, may be moreeitectively produced by the process of the invention of thisapplication, as will be presently described.

In the prior processes of hydrolyzing the mixed telomer alkoxyaluminurnchlorides, the hydrolyzing medium is an aqueous solution of hydrochloricor sulfuric acids, or water alone. While the hydrolyzing medium is beingvigorously stirred, the anhydrous telomer vallroxyaluminum chlorides areadded thereto so as to bring the telomer alkoxyaluminum chlorides intointimate agitative reactive contact with the aqueous hydrolyzing medium,thus efiecting within the resulting admixture the production of thetelomer alcohols in accord with the Equation 4 above. Thereupon, themixture is separated, as by settling, into two portions, an upperorganic portion containing the telomer alcohols and a lower aqueousportion. The latter is drawn off and the telomer alcohols recovered fromthe upper organic portion. The telomer alcohols are said to be sprungfrom the telomer alkoxyaluminum chlorides.

The prior process, while commercially operative for telomer alcoholshaving up to 12 carbon atoms, is not economically effective for telomeralcohols having from 12 to 30 or more carbon atoms, all of which aresolids at room temperatures, namely, 20 (3., since it is very difiicultto obtain by settling a good clean and complete phase eparation betweenthe organic and aqueous phases of the admixture, for the reason thatsolid gels of the solid telomer alcohols form in the admixture andcloudy, difiicultly separable phases result, requiring more time andgenerally further separation operations that cause low product yieldsand increased cost of the separation operation.

Extensive experimentation and tests have shown that as the chain lengthof the solid telomer alcohols increases, the difiiculty of phaseseparation because of gelation is increasingly greater, that betterseparations are obtained at higher temperatures than at lowertemperatures, but that at higher temperatures the telomer alcoholsdecompose and discolor and that even colorless telomer alcoholshydrolyzed at higher temperatures give straw-colored plasticizers whenesterified with phthalic anhydride.

The object of this invention is to effect economically in a short timeand at relatively low temperatures a good clean and practically completephase separation by settlin of the two-phase admixture resulting fromthe hydrolysis of higher telomer alkoxyaluminum chlorides by an aqueoushydrolyzing medium.

Applicants have in the invention of this application discovered a novel,highly effective and economical process for overcoming the inadequaciesof the prior processes enumerated in the preceding paragraphs, whichnovel process makes commercially practical (a) a good clean andpractically complete phase separation at reasonably low temperatures ina few minutes of time with a hi h yield of solid telomer alcohols, (b)colorless solid telomer alcohols, and (c) colorless plasticizers whenthe telomer alcohols are esterified with phthalic anhydride.

In carrying out the invention of this application, there is employed anovel hydrolyzing medium comprising Water, or water and an acid, and analcohol liquid at normal temperatures and having a boiling point lowerthan that of the solid telomer alcohol being produced, these alcoholsa's' a"c1ass being referred to. as liquid alcohols and alcohols havingfrom 2 to 10 carbon atoms being herein for convenience termed liquidlow-boil alcohols. The liquid alcohol is present in proportions rangingfrom 4 to 100 parts byweight of alcohol to 100 parts of the telomeralkoxyaluminum chlorides, normally from 30 to '75 parts by weight of theliquid alcohol are employed, the ratio of liquid alcohol to the telomeris not critical and preferably increases as the number of carbon atomsin the telomer alcohol increases. The hydrolyzing medium may alsocontain small proportions of sulfuric and hydrochloric acid, as in theprior processes, but it has been ascertained by extensive testing thatthese acid con stituents are not essential to the invention of thisapplication and may be omitted.

The telomer a koxyalurninum chlorides from which the telomer alcoholsare sprung, may be dispersed in the liquid organic anhydrous dispersantin which the telomer alkoxyaluminum chlorides were produced. Thesedispersants include the liquid alkanes, the liquid mixed alkanes, suchas Deobase kerosene and those resulting from the Fischer-Tropschprocess, the liquid cycloalkanes, the liquid benzene hydrocarbons,tetrahydrofuran, isopropyl ether and the like. Also included may beother compounds present at the end of the oxidation step producing thetelomer alkoxyaluminum chlorides. Alternatively, the telomeralkoxyaluminum chlorides may be practically free of any other compounds.

GENERAL EXAMPLE It is to be understood that the invention of thisapplication is not limited to any particular apparatus for the carryingout'of the process thereof. A suitable hydrolyzing reactor comprises afluid tight reaction vessel, such as a jacketed Pfaudler kettle,equipped with an electrically driven rotary stirrer; a thermometer;inlet and outlet connections, including an inlet for delivering to thehydrolyzer'the hydrolyzing medium, preferably in measured amount, asthrough a recording liquid meter, from a source of supply, as a storagetank; and an inlet for delivering the telomer alkoxyaluminum chlorides,preferably in measured amount as through a recording liquid meter toindicate rate and amount of flow; a reflux condenserfor venting vaporsfrom the top of the hydrolyzer and for condensing and returningcondensed vapors to the hydrolyzer; and a valved outlet connection fromthe bottom of the hydrolyzer. There is also provided means for heatingor cooling the hydrolyzer contents, such as the outside heat-transferjacket or inside heat-transfer coils, or both, for maintaining a desiredrange of temperatures of the hydrolyzer contents. Alternatively, thereflux condenser may be of the closed type, in which case the pressurewithin the hydrolyzer should be kept at a low level, and should notexceedlS to 20 p.s.i.g.

The hydrolyzing medium comprising water, or water and acid, and a liquidalcohol is charged into a hydrolyzer of the type hereinabove describedand the stirrer placed in operation. The hydrolyzing medium may be, butis not necessarily, heated to near, but not much above, the refluxtemperature, of lowest boiling constituent of the hydrolyzing medium.The I telomer alkoxyaluminum chlorides which may be, but are notnecessarily, preheated to about the temperature of the hydrolyzingmedium, are fed slowly into the hydrolyzer, with the agitationcontinuing'until the hydrolyzing action is completed, the exothermicheat of hydrolysis being removed by the cooling means. The hydrolyzingaction is almost instantaneous as the telomer alkoxyaluminum chloridesare stirred into the hydrolyzing medium. The stirrer is turned off andthe organic phase and the aqueous phase allowed to separate. Good cleanand complete separation of the two phases is obtained in about 5 tominutes. 5 minutes is suflicient. The heavier aqueous phase is withdrawnfrom the bottom of the hydrolyzer through Usually a valved outletconnection, Then the lighter organic phase, which includes the sprungtelomer alcohols, is withdrawn for further processing and recovery ofthe telomer alcohols. This is accomplished by the neutralizing, dryingand filtering of the sprung telomer alcohols. Where it is desired toseparate mixed telomer alcohols into the individual telomer alcohols,this further step is accomplished in the usual way by fractionaldistillation under vacuum of the mixed telomer alcohols.

EXAMPLE I The following example is illustrative of the process of thisinvention. Utilizing the apparatus and procedure described in theGeneral Example and starting with a tel omer alkoxyaluminumsesquichloride of the formula (C l-i O AlCl wherein theaverage value ofn is 14, and with a hydrolyzing medium comprising 140 grams of n-butanoladmixed with 280 grams of distilled water, first, charge thehydrolyzing'rnedium into the hydrolyzer, and place the stirrer inoperation, then, add gradually and slowly into the top of the hydrolyzer440 grams of the said telomer alkoxyaluminum sesqui'chloride, the heat.of hydrolysis raising the temperature of the hydrolyzer contents whichfor highest efficiency should be maintained at about C. to C., i.e., ata temperature not higher than about the boiling point of any constituentin the hydrolyzer, by' carrying away the heat of hydrolysis through theheat-transfer devices.v Higher or'lower temperatures, however, may beemployed. When the hydrolyzing reaction, which is normally very rapid,is completed, the stirrer is turned off and the hydrolyzer contentsallowed to stand to separate it into two phases, a lighter upper organicphase which contains the telomer alcohols as well as a major part of then-butanol, and a heavier aqueous phase. The lighter organic phase isthen isolated and the telomer alcohols recovered therefrom, as

by fractional distillation, and analyzed with the following results:

Table I .T elomer alcohols yield EXAMPLES 11 TO v Several differenttelomer alkoxyaluminum sesquichlorides (TAS) were isolated andeach'hydrolyzed separately with a hydrolyzing medium (HM) consisting ofn-butanol and water, followingthe procedure of Example I, the data ofeach of these operations being tabulated below.

EXAMPLE II Parts by weight, grams (a) TAS=(C1ZH25O)L5AICIL5 (b)HM=n-Butanol 15 And water 50 Phase separation time, 10 minutes Percentyield C H OH=98.8.

EXAMPLE III Recipe:

(a) TAS: I

n-Butanolfi 20- And' water Phase separation time, 10 minutes.

Percent yield C H O H:98.8.

5 EXAMPLE IV Parts by Weight, grams Recipe:

(a) TAS:

24 49 )1.5 1,5 (b) HM:

n-Butanol 50 And water 75 Phase separation time, 10 minutes. Percentyield C H OH=98.5.

EXAMPLE V Recipe:

(a) TAS:

3u e1 )1.5 1.5 100 (b) HM:

n-Butanol 60 And Water 100 Phase separation time, 10 minutes. Percentyield C I-i OI-I==97.8.

EXAMPLES VI TO VIII In the following series of tests, a number oftelomer alkyl aluminum sesquichlorides were oxid zed in a liquiddispersant comprising heptane and potassium chloride to produce telomeralkoxyaluminum sesquichloride dispersed in the liquid dispersant and theletter was hydrolyzed as described in Example I in a hydrolyzing mediumcomprising water, n-butanol and sulfuric acid, producing telomeralcohols, all as indicated below:

EXAMPLE VI Parts by Recipe: weight, grams (a) TAS:

( 10 21 )1.5 1.5 100 Heptane 30 KCl 10 E (b) HM:

Water 150 n-Butanol 4 Sulfuric acid 20 174 Phase separation time, 5minutes. Percent yield C I-I OH=98.4.

EXAMPLE VII Recipe:

(a) TAS:

12 25 )1.5 1.5 100 Heptane 32 KCl m (b) HM:

Water 130 n-Butanol 5 Sulfuric acid 20 155 Phase separation time, 5minutes. Percent yield C H OH=98.9.

EXAMPLE VIII Recipe:

(a) TAS:

31 )1.5 1.5 190 Heptane 35 KCl 10 m (b) HM: Water 120 n-Butanol 10Sulfuric acid 150 Phase separation time, 5 minutes. PercentC15H31OH:99.3-

It is clearly demonstrated in the above Examples II to VIII that thehydrolysis of telomer alkoxyaluminum sesquichlorides, including theseparation of the organic and aqueous phases, is by the process of thisinvention carried out in a short time to produce a high yield of telomeralcohols.

As has been hereinabove indicated, the longer the alkyl chain of thetelomer alcohol the more difficult it is to effect the phase separationessential to spring the telomer alcohols from the hydrolyzing medium. Toillustrate the effectiveness of the hydrolyzing medium comprising otherlow-boil alcohols and water, the following series of tests were runutilizing telomer alkoxyalurninum sesquichloride having 24 carbon atoms,namely,

EXAMPLE IX Parts by Recipe: Weight, grams 24 49 )L5 l.5 1% (b) HM:

Water Ethanol (B.P. 78.5 C.) 75

175 Phase separation time, 5 minutes. Percent yield C H OH=99.2.

EXAMPLE X Recipe 24 9 )1.5 1.5 lQQ (b) HM: Water 100 n-Propanol (B.P.972 C.) 40

Phase separation time, 5 minutes. Percent yield C H OH=98.7.

EXAMPLE XI Recipe:

(b) HM: Water 100 n-Pentanol (B.P. 137.8 C.) 60

Phase separation time, 5 minutes. Percent yield C H OH:98.5.

EXAMPLE XII Recipe:

( 24 49 )1.5 1.5 w (b) HM: W'ater 100 n-Hexanol (B.P. 157 C.) 40

140 Phase separation time, 5 minutes. Percent yield C H OH:99.3.

EXAMPLE XIII Recipe:

( TAS: 24 4Q )1.5 1.5 E (b) HM: Water 100 n-Heptanol (B.P. 156 C.) 75

Phase separation time, 5 minutes. Percent yield C H OH=981 Percent yieldC I-I, H:98.7.'

As is clearly shown in Examples I to XIV, above, the added low boilingliquid alcohols may be added in amounts as low as 4% to as high as 100%,by weight,

of the telomer alkoxy-aluminum sesquichloride (TAS) to yield from 98% toas high as 99.7% of the desired solid alcohol. A summary of Weightsof'constituents disclosed in the above Examples I to XIV clearlydemonstrates this wide variability in the percentages of low boilingalcohol needed.

ployed may be varied, and that equivalent materials may 7 be employedwhere desirable, without departing from the spirit and scope of theinvention as defined in the appended claims.

What we claim is: 1. A process for the manufacture of higher alkylhydrocarbon alcohols that are solids at room temperatures, which processcomprises stirring alkoxyaluminum sesquichlorides of the'empiricalformula (C H O) AlCl in which x and y are each numerical values rangingfrom 2.7 to 0.3 and whose sum is 3 and in which n ranges from 12 to 30,into a hydrolyzing liquid medium consisting essentially of (i) water and(ii) an alcohol which is liquid at room temperatures selected from theclass consisting of alkyl monohydric hydrocarbon alcohols having from 2to 10 carbon atoms; the said liquid alcohol being present in from 4% to100% by weight of the alkoxyaluminum sesquichloride; continuing thestirring until all of the alkoxyaluminum sesquichloride has beenintimately admixed into the hydrolyzing liquids, then allowing theresulting mixture to stand, in which condition it quickly 7 7 Table ofweights of constituents used in Ex. I to XIV TAS A W HM A/TAS, A/HM,HM/TAS, Ex. Sesqui- Liquid Water Hydropercent percent percent chloridealcohol lyzing 1 medium Other added liquid alcohols than the liquidlow-boil alcohols referred to in the above specific examples areoperable in the process of the invention of this application to bringabout a clean and complete separation of the organic phase andtheaqueous phase of the mixture produced in the hydrolysis of telomeralkoxyaluminum chlorides. The ease of separating out of the added liquidalcohols from the telomer alcohols produced may be determinative of thespecific added alcohol to be employed. Experience has indicated that theadded liquid alcohol should have a boiling point at least 25 C. lowerthan that of the telomer alcohols being produced and that the liquidlow-boil normal alcohols having from 2 to 8 carbon atoms are preferablein the production of the process of this invention of telomer alcoholswhich are solids at normaltemperatures, viz. the C and higher alcohols.

Other liquid alcohols which have been found to be effective in theprocess of the invention of this application, not specifically mentionedin the above examples, are the monohydric alcohols, such as 2-propanol,B.P. 82.4 C.; sec-butanol, B.P. 99.5 C.; tert.-butanol, B.P. 825 C.;tert.-pentanol, B.P l0l.8 C.; 2-ethylbutanol, B.P. 148.9 C.; 3-heptanol,B.P. 156 C.; 2-octanol, B.P. 178.2 C.; n-nonanol, B.P. 215 C.;n-decanol, B.P. 232j C.; and also polyhydric alcohols, such as ethyleneglycol, B.P. 197.2" C.; propylene glycol, B.P. 182 C.; 1,3-butyleneglycol, 207 C.; hexylene glycol, B.P. 198 C.; glycerol,

' B.P. 290 C.; and the like.

separates into two distinct layers, namely, an upper liquid organicportion containing the higher solid alcohol produced and a lower aqueouslayer; and fractionally distilling the said upper organic portion toisolate the higher solid alcohols thus produced.

2. The process defined in claim 1 in which the liquid 7 V ous liquid ofthe hydrolyzing liquid is water. I

, 6. The process defined in claim 1 in which the liquid alcohol of thehydrolyzing liquid is a butanol and the aqueous liquid of thehydrolyzing liquid is water.

7. The process for the manufacture of a higher alkyl 7 alcohol that issolid at room temperature and is within the empirical formula C H OH, inwhich n ranges from 12 to 30, which process comprises admixing withstirring an alkoxyaluminum sesquichloride of the empirical formula (C HO) AlCl in which x and y are numerical values ranging from 2.7 to 0.3and whose sum is 3 and in which n ranges from 12 to 30, into ahydrolyzing liquid medium consisting essentially of (i) an aqueousliquid selected from the class consisting of water and dilute watersolutions of'amineral acid, and (ii) liquid alcohol selected from theclass consisting of alkyl monohydric hydrocarbon alcohol'having from 2to 10 carbon atoms; the ratio of the weight of liquid alcohol to theweight of hydrolyzing liquid medium ranging from 2.5 parts by weight ofthe liquid alcohol to 75 parts by weight of the said hydrolyzing medium;continuing the stirring until all of the alkoxyaluminum sesquichloridehas been intimately admixed with the hydrolyzing medium; then allowingthe resulting admixture to stand until there is a practically completeand rapid phase separation thereof into an upper organic portion and alower aqueous portion; isolating the said upper organic portion andrecoven'ng from said upper organic portion the solid higher alcohol thusproduced.

8. The process defined in claim 7 in which the liquid alcohol of thehydrolyzing liquid is ethanol.

9. The process defined in claim 7 in which the liquid alcohol of thehydrolyzing liquid is butanol.

10. The process defined in claim 7 in which the aqueous liquid is water.

References Cited by the Examiner UNITED STATES PATENTS 7/1957 Sonntag260632 12/ 1958 Kirshenbaum et al. 260-632 X FOREIGN PATENTS 12/ 1958Great Britain.

LEON ZITVER, Primary Examiner.

15 C. B. PARKER, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,247,264 April 19, 196

Warren L. Beears et a1.

ror appears in the above numbered pat- It is hereby certified that erthe said Letters Patent should read as ent requiring correction and thatcorrected below.

Column 4, line 16, for [C H O A1c1 read (C H 0) A1Cl EXAMPLE II, insertRecipe: as a heading to the first column; line 65, for "C H OH=98.8"

read (C H O) l A1Cl 1 5 line 75 for "C H OH=98 8" read C H OH=98.8column 5, line 75, after "Percent" insert Yield Signed and sealed this14th day of November 1967 (SEAL) Attest:

EDWARD J. BRENNER Edward M. Fletcher, Jr.

Commissioner of Patents Attesting Officer

1. A PROCESS FOR THE MANUFACTURE OF HIGHER ALKYL HYDROCARBON ALCOHOLSTHAT ARE SOLIDS AT ROOM TEMPERATURES, WHICH PROCESS COMPRISES STIRRINGALKOXYALUMINUM SESQUICHLORIDES OF THE EMPIRICAL FORMULA(CNH2N+1O)XALCLY, IN WHICH X AND Y ARE EACH NUMERICAL VALUES RANGINGFROM 2.7 TO 0.3 AND WHOSE SUM IS 3 AND IS WHICH N RANGES FROM 12 TO 30,INTO A HYDROLYZING LIQUID MEDIUM CONSISTING ESSENTIALLY OF (I) WATER AND(II) AN ALCOHOL WHICH IS LIQUID AT ROOM TEMPERATURES SELECTED FROM THECLASS CONSISTING OF ALKYL MONOHYDRIC HYDROCARBON ALCOHOLS HAVING FROM 2TO 10 CARBON ATOMS; THE SAID LIQUID ALCOHOL BEING PRESENT IN FROM 4% TO100% BY WEIGHT OF THE ALKOXYALUMINUM SESQUICHLORIDE; CONTINUING THESTIRRING UNTIL ALL OF THE ALKOXYALUMINUM SESQUICHLORIDE HAS BEENINTIMATELY ADMIXED INTO THE HYDROLYZING LIQUIDS, THEN ALLOWING THERESULTING MIXUTRE TO STAND, IN WHICH CONDITION IT QUICKLY SEPARATES INTOTWO DISTINCT LAYERS, NAMELY, AN UPPER LIQUID ORGANIC PORTION CONTAININGTHE HIGHER SOLID ALCOHOL PRODUCED AND A LOWER AQUEOUS LAYER; ANDFRACTIONALLY DISTILLING THE SAID UPPER ORGANIC PORTION TO ISOLATE THEHIGHER SOLID ALCOHOLS THUS PRODUCED.